JP2016531135A - Etheramines based on alkoxylated glycerol or trimethylolpropane - Google Patents

Abstract

The present invention relates to an ether amine of the general formula (I) based on glycerin or trimethylolpropane, wherein R is H or ethyl, K is 0 or 1, and A is , C 2 -C 18 straight or branched alkylene, each A may be the same or different, at least one A represents a straight or branched C 4 -alkylene group, x , Y and z are in the range of 3-100, x is 1 or more, y is 1 or more, z is 1 or more, Z is NH2 or OH, but at least per molecule And two Z are NH 2) and a method for producing the same.

Description

The present invention relates to etheramines based on alkoxylated glycerin or trimethylolpropane, said etheramine comprising at least one linear or branched C ₄ -alkylene group.

  Due to the prevalence of easy-care fabrics made of synthetic fibers, increased energy costs, and environmental concerns among detergent users, washing with hot water, which has been popular in the past, is now given priority to washing fabrics with cold water. ing. Furthermore, many commercial laundry detergents are advertised as suitable for washing fabrics at 30 ° C. or 40 ° C., or even room temperature. The demand for low-temperature detergents is particularly high in order to achieve a satisfactory cleaning as compared to those washed with hot water at such a low temperature.

  In order to improve the detergency of conventional surfactants, it is known to include some additives in the detergent composition to improve oil stain removal at low temperatures below 60 ° C.

  Also, since oil stain removal is difficult, there is a continuing need for cleaning compositions that remove oil stains from fabrics and other soiled materials. Conventional cleaning compositions for oil and fat removal typically utilize a variety of amine compounds that tend to have a very negative effect on whiteness. As a result, there is still a continuing need for superior amine compositions that provide superior oil removal from fabrics and other soiled materials while not adversely affecting clay cleaning. ing. These amine compositions should also have a suitable toxicity profile, which allows them to be used for home use.

  DE 1 643 426 A1 discloses a process for the preparation of polyoxyalkylene polyamines, in which a polyalcohol having 3 to 8 hydroxyl groups is reacted with a C1 to C18 alkylene oxide, followed by an amine in the presence of a catalyst. It becomes.

  EP 1 502 913 A1 discloses a process for preparing polyoxyalkylene triamines by contacting polyoxyalkylene triols with ammonia and hydrogen in the presence of a catalyst. The polyoxyalkylene triol includes an alkylene group having 2 to 6 carbon atoms.

  WO 01/76729 A2 relates to a composition comprising a multifunctional polyetheramine having at least two amine groups per molecule, the polyetheramine comprising an alkylene group having 2 to 3 carbon atoms.

  US 4,609,683 discloses quasi-propolymers prepared by reacting aromatic isocyanates with polyoxyalkylene triamines and isatoic anhydride.

DE 1 643 426 A1 EP 1 502 913 A1 WO 01/76729 A2 US 4,609,683

  The objective of this invention is providing the compound which improves the washing | cleaning performance of a detergent at low temperature, ie, the temperature of 30 degrees C or less.

式中、
Ｒは、Ｈ又はエチルであり、
Ｋは、０又は１であり、
Ａは、Ｃ_２〜Ｃ_１８の炭素原子を有する直鎖又は分岐アルキレンを示し、
Ａは、それぞれ、同一又は異なるものであってもよく、
少なくとも１つのＡが、直鎖又は分岐Ｃ_４−アルキレン基を示し、
ｘ、ｙ及びｚの合計は、３〜１００の範囲であり、
ｘは１以上であり、ｙは１以上であり、ｚは１以上であり、
ＺはＮＨ２又はＯＨであるが、１分子当たり少なくとも２つのＺがＮＨ２であり、
好ましくはＺはＮＨ２である。 This object is achieved by the ether amines of the general formula (I)

Where
R is H or ethyl;
K is 0 or 1;
A represents a linear or branched alkylene having C _{2 to} C ₁₈ carbon atoms,
A may be the same or different,
At least one A is a linear or branched C ₄ - represents an alkylene group,
the sum of x, y and z ranges from 3 to 100;
x is 1 or more, y is 1 or more, z is 1 or more,
Z is NH2 or OH, but at least two Z per molecule are NH2,
Preferably Z is NH2.

In a preferred embodiment, at least three A are linear or branched C ₄ -alkylene groups. In other embodiments, all A groups are linear or branched C ₄ -alkylene groups.

  Preferably, the sum of x, y and z is in the range of 3-30, more preferably in the range of 3-10, most preferably in the range of 5-10.

The ether amine of the general formula (I) has the following steps:
a) reacting glycerin or 1,1,1-trimethylolpropane with C ₄ -alkylene oxide and optionally with C ₂ -C ₁₈ -alkylene oxide, wherein glycerin and C ₄ -alkylene oxide The molar ratio is in the range of 1: 3 to 1:10, and
b) aminating the alkoxylated glycerin with ammonia.
Is obtained by a method comprising

Alkoxylation In a preferred embodiment, the molar ratio of glycerin or 1,1,1-trimethylolpropane to C ₂ -C ₁₈ -alkylene oxide and in particular butylene oxide ranges from 1: 3 to 1: 6. .

Alkoxylated triols are obtained by reaction of glycerin or 1,1,1-trimethylolpropane with C ₂ -C ₁₈ -alkylene oxide and are carried out by common alkoxylation means known in the art.

Alkoxylated glycerin or 1,1,1-trimethylolpropane is produced by a known method in which glycerin or 1,1,1-trimethylolpropane is reacted with an alkylene oxide. Suitable alkylene oxides, C 2 _-C 18 _- alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, pentene oxide, hexene oxide, Desen'okishido is dodecene or the like.

_Preferably, C 2 _{-C 18} - alkylene oxides are ethylene oxide, propylene oxide and mixtures thereof.

  Glycerin or 1,1,1-trimethylolpropane is reacted with only one alkylene oxide or a combination of two or more different alkylene oxides. Using two or more different alkylene oxides, the resulting alkoxylation is obtained in a block-wise structure or a random structure.

The molar ratio of glycerin or 1,1,1-trimethylolpropane in which the alkoxylation reaction takes place to C ₄ -alkylene oxide and optionally C ₂ -C ₁₈ -alkylene oxide ranges from 1: 3 to 1:10. Preferably, it is in the range of 1: 3 to 1: 6. In another embodiment, the molar ratio of glycerin or 1,1,1-trimethylolpropane in which the alkoxylation reaction takes place to C ₄ -alkylene oxide and optionally C ₂ -C ₁₈ -alkylene oxide is 1: 5. It is in the range of ˜1: 10.

  Generally, this reaction is carried out in an aqueous solution in the presence of a catalyst at a reaction temperature of about 70 ° C. to about 200 ° C., preferably about 80 ° C. to about 160 ° C. This reaction is carried out at a pressure below about 10 bar, in particular below 8 bar.

Examples of suitable catalysts include basic catalysts such as alkali metal and alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal alkoxides, especially sodium and potassium C _1- C ₄ -alkoxides such as sodium methoxide, sodium ethoxide and potassium tert-butoxide, alkali metal and alkaline earth metal hydrides such as sodium hydride and calcium hydride, and alkali metal carbonates such as sodium carbonate And potassium carbonate. Alkali metal hydroxides are preferred, especially potassium hydroxide and sodium hydroxide. The general use amount of this base is from 0.05% by weight to 10% by weight, in particular from 0.1% by weight to 2% by weight, based on the total of polyalkyleneimine and alkylene oxide.

Amination Amination is carried out in the presence of a catalyst containing copper, nickel or cobalt.

  Before being reduced by hydrogen, the catalytically active material of the catalyst contains oxygen compounds of aluminum, copper, nickel and cobalt, and is 0.2% to 5.0% of the oxygen compound of tin (calculated by SnO). % Range.

The ether amines according to general formula (I) are obtained by reductive amination of alkoxylated glycerol or 1,1,1-trimethylolpropane with ammonia in the presence of hydrogen and nickel containing catalysts. Suitable catalysts are described in WO 2011/067199 A1, WO 2011/0667200 A1 and EP 0696572 B1. Preferred catalysts are catalysts containing supported copper, nickel or cobalt, wherein the catalytically active material of the catalyst contains copper, nickel and cobalt oxygen compounds before being reduced by hydrogen, and tin oxygen compounds (SnO In the range of 0.2 mass% to 5.0 mass%). Further preferred catalysts are catalysts containing supported copper, nickel or cobalt, the catalytically active material of the catalyst comprising oxygen compounds of aluminum, copper, nickel, cobalt and tin before being reduced by hydrogen, and yttrium , Lanthanum, cerium and / or hafnium oxygen compounds (calculated respectively by Y ₂ O ₃ , La ₂ O ₃ , Ce ₂ O ₃ and Hf ₂ O ₃ ) from 0.2% by mass to 5.0% by mass % Range. Other preferred catalysts are zirconium, copper, nickel catalysts, and the catalytically active composition comprises 20% to 85% by weight of oxygen containing zirconium compound (calculated with ZrO ₂ ), 1% to 30% by weight. % Oxygen-containing copper compound (calculated with CuO), 30% to 70% oxygen-containing nickel compound (calculated with NiO), 0.1% to 5% oxygen-containing aluminum And / or manganese compounds (calculated with Al ₂ O ₃ and MnO ₂ respectively).

  In the reductive amination step, both supported and unsupported catalysts are used. Supported catalysts include support materials known to those skilled in the art, including, but not limited to, known forms of alumina, silica, charcoal, carbon, graphite, clay and mordenite using techniques well known in the art. Obtained by the molecular sieve used to deposit the metal component of the catalyst composition on top and to provide a supported catalyst. When the catalyst is supported, the support particles of the catalyst may be geometric, for example regular or irregular spheres, tablets or cylinders.

  It is carried out in continuous mode or discontinuous mode, for example in an autoclave, tubular reactor or fixed bed reactor. Also, the reactor design is not narrowly limited. The feed to it may be upflow or downflow, and the design characteristics in the reactor that optimize the plug flow in the reactor are used.

  Under the reaction conditions of amination, by-products containing secondary or tertiary amino functions can be produced. Secondary amino acids are obtained, for example, by reacting fully or partially aminated diols with other fully and / or partially aminated diols. Tertiary amino is obtained, for example, by reacting secondary amino with other fully and / or partially aminated diols.

  The degree of amination is between 67% and 100%, preferably 85% to 100%.

  The degree of amination is calculated from the total amine number (AZ) divided by the sum of the total acetylable number (AC) and the tertiary amine number (tert.AZ) and multiplied by 100 (total Is AZx100 / (AC + tert.AZ)).

  The total amine number (AZ) is measured by DIN 16945.

  The total acetylable value (AC) is measured by DIN 53240.

  Secondary amines and tertiary amines are measured by ASTM D2074-07.

  The hydroxyl number is measured by (total acetylable value + tertiary amine number) −total amine number.

  In another preferred embodiment, the ether amine of the present invention is also further reacted with an acid. The acids are citric acid, lactic acid, sulfuric acid, methanesulfonic acid, hydrogen chloride, phosphoric acid, formic acid, acetic acid, propionic acid, valeric acid, oxalic acid, succinic acid, adipic acid, sebacic acid, glutaric acid, glucaric acid, tartaric acid , Malic acid, benzoic acid, salicylic acid, phthalic acid, oleic acid, stearic acid and mixtures thereof are selected from the group. In another embodiment, the ether amine of the present invention may be obtained in the protonated state, for example from a linear alkylbenzene sulfonic acid, and may have a surfactant as a counter ion.

application:
The ether amine mixtures of the present invention are used in personal care, particularly shampoos, body soap formulations and cleaning compositions.

  They are also used as curing agents for epoxy resins or as reactants in polyurethanes, polyureas, epoxy resins, polyamides as well as during the production of polymers.

  The ether amines of the present invention have proven to be effective in removing dirt, especially fats and oils, from dirty materials. Also, the cleaning compositions with ether amines of the present invention have no cleaning negatives compared to conventional amine cleaning compositions for hydrophilic and bleachable soils such as coffee, tea, wine or fine particles. . Furthermore, in removing soil from white fabrics, the cleaning compositions having the ether amine of the present invention do not cause the whiteness disadvantages caused by commercial amine cleaning compositions.

  Another advantage of a cleaning composition comprising the ether amine of the present invention is that oil stains can be removed in a cold water cleaning solution after cold water washing. Without being limited to the theory, the cold water washing solution causes hardening or solidification of the oil and fat, and has an effect of making it difficult to remove the oil and fat from the fiber in particular. However, cleaning compositions having an ether amine mixture according to general formula (I) are surprisingly effective when used for cold water cleaning.

  As used herein, the term “cleaning composition” includes compositions and formulations designed to clean dirty materials. Such compositions include laundry cleaning compositions and detergents, softener compositions, fabric enhancing compositions, fabric freshening compositions, laundry prewashes, laundry prewashes, laundry Additives, spray products, dry cleaning agents or compositions, laundry rinse additives, laundry additives, post-rinse fabric treatment, ironing aids, unit dose compositions, delays Delayed delivery formulations, liquid dishwashing compositions, detergents contained on or in porous substrates or non-woven sheets, automatic dishwashing agents, hard surface cleaners, and for those skilled in the art because of the description herein It includes other suitable forms that will be apparent. Such a composition may be used as a pre-wash or post-wash treatment, may be added during the wash cycle of a rinse or wash run, and may be used in homecare cleaning applications. . The cleaning composition has a form selected from liquid, powder, single-phase or multi-phase unit dose, pouch, tablet, gel, paste, stick or flake Also good.

  The cleaning compositions described herein can be from about 0.1% to about 10% by weight of the composition, in some examples from about 0.2% to about 5%, in other embodiments from about 0%. It may contain from 5% to about 3% by weight of ether amines of the general formula I.

Surfactant system The cleaning composition comprises a sufficient amount of a surfactant system to provide the desired cleaning properties. In embodiments, the cleaning composition comprises about 1% to about 70% surfactant system by weight of the composition. In other embodiments, the cleaning composition comprises from about 2% to about 60% by weight of the surfactant amount of the composition material. In a further embodiment, the cleaning composition comprises about 5% to about 30% surfactant system by weight of the composition.

  Surfactant systems include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, ampholytic surfactants and their A detersive surfactant selected from the mixture may be included. It is understood in the art that these conventional techniques include any surfactant or mixture of surfactants that provide cleaning, soil removal, or laundry benefits to soiled materials.

Auxiliary Cleaning Additive The cleaning composition of the present invention may also include an auxiliary cleaning additive. Suitable auxiliary cleaning additives include builders, structurants or thickeners, clay soil removal / anti-redeposition agents, polymeric soil release agents, polymeric dispersants, high Molecular fat cleaning agent, enzyme, enzyme stabilization system, bleach compound, bleach, bleach activator, bleach catalyst, whitening agent, dye, hueing agents, dye transfer inhibitor, complexing agent, foam inhibitor (Suds supressors), softeners and fragrances.

Method of Use The present invention includes a method of cleaning dirty material. As will be appreciated by those skilled in the art, the cleaning compositions of the present invention are suitable for use in laundry pretreatment, laundry washing, and home care.

  Such methods include, but are not limited to, contacting at least a portion of the soiled material with a cleaning composition dissolved in a neat form or wash water, and optionally rinsing the soiled material thereafter. including. The soiled material may undergo a cleaning step prior to any rinsing step.

  In use for laundry pretreatment, the method may include contacting the soiled fabric with a cleaning composition described herein. Following pretreatment, the soiled fabric may be washed in a washing machine or otherwise rinsed.

  The machine wash method may include the step of treating soiled laundry with a wash solution in a washing machine in which an effective amount of the machine wash composition of the present invention has been dissolved or applied. “Effective amount” of a cleaning composition means that about 20 g to about 300 g of product is dissolved or dispersed in a laundry solution of about 5 liters to about 65 liters in volume. The water temperature may range from about 5 ° C to about 100 ° C. The ratio of water to soiled material (eg, fibers) may be about 1: 1 to about 20: 1. In the textile laundry composition of the present invention, the level of the amount used is not only the type and severity of dirt and stains, but also the washing water temperature, the volume of washing water, the type of washing machine (for example, top loader, front loader, top load Depends on the loader and vertical fully automatic Japanese washing machine.

  Here, the cleaning composition is used for laundering fabrics at reduced washing temperatures. The method for washing these fibers includes a step of adding a laundry washing composition into water to form a washing aqueous solution, and a step of putting a washing fabric into the washing aqueous solution, wherein the washing aqueous solution is about 0 ° C to about 30 ° C, It has a temperature of about 0 ° C to about 25 ° C, or about 0 ° C to about 15 ° C. The fabric may be contacted with water before, after, or simultaneously with the laundry cleaning composition and water.

  Another method includes contacting the soiled material with a nonwoven substrate impregnated with the cleaning composition of the embodiment. As used herein, a “nonwoven substrate” can include any conventional fashioned nonwoven sheet or fabric having suitable basis mass, caliper (thickness), absorbent and strength properties. Non-limiting examples of suitable commercially available nonwoven substrates include those sold under the trade names SONTARA® from DuPont and POLYWEB® from James River Corp.

  A hand washing method and a combination of a semi-automatic washing machine and hand washing are also included.

Machine wash methods for dishware Machine wash or hand washing methods for dirty dishes, tableware, silverware or other kitchen utensils are included. One machine cleaning method comprises the steps of treating tableware, tableware, silver tableware or other kitchen utensils soiled by an aqueous solution dissolved or applied thereto with an effective amount of a tableware machine cleaning composition according to the present invention. Including. An effective amount of a tableware machine cleaning composition is meant to dissolve or disperse about 8 g to about 60 g of product in a wash liquor of about 3 liters to about 10 liters volume.

  One hand washing method involves dissolving the cleaning composition in a container with water, then contacting the soiled dishware, tableware, silverware or other kitchen utensils with the dishwashing liquid, and then soiling. Hand washing, wiping or rinsing dishes, tableware, silverware or other kitchen utensils. Other hand washing methods include applying the cleaning composition directly to dirty dishes, tableware, silverware or other kitchen utensils, and then dirty dishes, tableware, silverware or other kitchenware. Includes hand washing, wiping or rinsing equipment. In embodiments, an effective amount of hand wash cleaning composition is dissolved in water and is from about 0.5 ml to about 20 ml.

Composition Packaging The cleaning compositions described herein are packaged in any suitable container, including those comprised of paper, cardboard, plastic material and any suitable sheet. Optional packaging types are listed in European Application No. 94921505.7.

Multi-compartment sachet additive The cleaning compositions described herein may also be packaged as multi-compartment cleaning compositions.

Synthesis Examples In the examples, the following abbreviations are used:
BuO is butylene oxide;
PO is propylene oxide.

Example 1: 1 mol glycerin + 3 mol BuO + 3 mol PO, amination a) 1 mol glycerin + 3 mol BuO + 3 mol PO
In a 3.5 liter autoclave, 95.0 g glycerin and 1.0 g potassium tert. -Butyrate was mixed. The autoclave was purged with nitrogen three times and heated to 140 ° C. Within 90 minutes, 223.0 g of butylene oxide was added. The mixture was left to react at 140 ° C. for 5 hours. Thereafter, 179.7 g of propylene oxide was added in portions within 1 hour. In order to complete the reaction, the mixture was left to react at 140 ° C. for a further 3 hours. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80 ° C. The catalyst was removed by adding 4.9 g of synthetic magnesium silicate (Macrosorb MP5plus, Ineos Silicas), stirring at 100 ° C. for 2 hours and filtering.

  A yellow oil (490.0 g, hydroxyl number: 314.5 mg KOH / g) was obtained.

b) 1 mol glycerin + 3 mol BuO + 3 mol PO, amination In a 9 liter autoclave in the presence of 200 mL solid catalyst as described in EP 0696572B1, 350 mL of the triol mixture obtained in Example 1-a, 1200 mL Of THF and 1500 g of ammonia were mixed. The catalyst contained nickel, cobalt, copper, molybdenum and zirconium and was in the form of 3 mm × 3 mm tablets. The autoclave was purified with nitrogen, and the reaction was started by heating the autoclave. The reaction mixture was stirred at 205 ° C. for 15 hours and the total pressure was maintained at 280 bar with purified hydrogen during the entire reductive amination step. After cooling the autoclave, the final product was collected, filtered, stripped of excess ammonia, and stripped on a rotary evaporator to remove light amines and water. A total of 350-400 g of low-color etheramine mixture was recovered. The analysis results are shown in Table 1.

Example 2: 1 mol glycerin + 3 mol PO + 3 mol BuO, amination a) 1 mol glycerin + 3 mol PO + 3 mol BuO
In a 3.5 liter autoclave, 88.1 g glycerin and 0.9 g potassium tert. -Butyrate was mixed. The autoclave was purged with nitrogen three times and heated to 140 ° C. Within one hour, 166.6 g of propylene oxide was added. The mixture was left to react at 140 ° C. for 3 hours. Thereafter, 206.8 g of butylene oxide was added in portions within 1 hour. In order to complete the reaction, the mixture was left to react at 140 ° C. for a further 3 hours. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80 ° C. The catalyst was removed by adding 4.4 g of Macrosorb MP5plus, stirring at 100 ° C. for 2 hours and filtering.

  A yellow oil (410.0 g, hydroxyl number: 336.5 mg KOH / g) was obtained.

b) 1 mol glycerin + 3 mol PO + 3 mol BuO, amination in a 9 liter autoclave in the presence of 200 mL solid catalyst as described in EP 0696572B1 350 mL of the triol mixture obtained in Example 2-a, 1200 mL Of THF and 1500 g of ammonia were mixed. The catalyst contained nickel, cobalt, copper, molybdenum and zirconium and was in the form of 3 mm × 3 mm tablets. The autoclave was purified with nitrogen, and the reaction was started by heating the autoclave. The reaction mixture was stirred at 205 ° C. for 15 hours and the total pressure was maintained at 280 bar with purified hydrogen during the entire reductive amination step. After cooling the autoclave, the final product was collected, filtered, stripped of excess ammonia, and stripped on a rotary evaporator to remove light amines and water. A total of 300-350 g of low color ether amine mixture was recovered. The analysis results are shown in Table 2.

Example 3: 1 mol glycerin + 6 mol BuO, amination a) 1 mol glycerin + 6 mol BuO
In a 3.5 liter autoclave, 103.4 g glycerin and 1.2 g potassium tert. -Butyrate was mixed. The autoclave was purged with nitrogen three times and heated to 140 ° C. Within 2 hours 485.5 g of butylene oxide was added. To complete the reaction, the mixture was left to react for a further 7 hours at 140 ° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80 ° C. The catalyst was removed by adding 5.9 g Macrosorb MP5plus, stirring at 100 ° C. for 2 hours and filtering.

  A yellow oil (589.0 g, hydroxyl number: 285.0 mg KOH / g) was obtained.

a) Glycerin + 6 mol BuO, amination 500 g of the triol mixture obtained in Example 3-a, 1200 mL of THF and 1500 g of ammonia in the presence of 200 mL of solid catalyst as described in EP 0696572B1 in a 9 liter autoclave. Were mixed. The catalyst contained nickel, cobalt, copper, molybdenum and zirconium and was in the form of 3 mm × 3 mm tablets. The autoclave was purified with nitrogen, and the reaction was started by heating the autoclave. The reaction mixture was stirred at 205 ° C. for 15 hours and the total pressure was maintained at 280 bar with purified hydrogen during the entire reductive amination step. After cooling the autoclave, the final product was collected, filtered, stripped of excess ammonia, and stripped on a rotary evaporator to remove light amines and water. A total of 450 g of low color ether amine mixture was recovered. The analysis results are shown in Table 3.

Example 4: 1 mol glycerin + 4.2 mol PO + 1.8 mol BuO, amination a) 1 mol glycerin + 4.2 mol PO + 1.8 mol BuO
In a 3.5 liter autoclave, 88.9 g glycerin and 0.9 g potassium tert. -Butyrate was mixed. The autoclave was purged with nitrogen three times and heated to 140 ° C. Within 1.5 hours, 235.4 g of propylene oxide was added. The mixture was left to react at 140 ° C. for 3 hours. Thereafter, 125.2 g of butylene oxide was added in portions within 1 hour. In order to complete the reaction, the mixture was left to react for a further 5 hours at 140 ° C. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80 ° C. The catalyst was removed by adding 4.7 g of Macrosorb MP5plus, stirring at 100 ° C. for 2 hours and filtering.

  A yellow oil (470.0 g, hydroxyl number: 312.1 mg KOH / g) was obtained.

b) 1 mol glycerin + 4.2 mol PO + 1.8 mol BuO, amination Obtained in 350 mL of Example 4-a in the presence of 200 mL of solid catalyst as described in EP 0696572B1 in a 9 liter autoclave. Triol mixture, 1200 mL THF and 1500 g ammonia were mixed. The catalyst contained nickel, cobalt, copper, molybdenum and zirconium and was in the form of 3 mm × 3 mm tablets. The autoclave was purified with nitrogen, and the reaction was started by heating the autoclave. The reaction mixture was stirred at 205 ° C. for 15 hours and the total pressure was maintained at 280 bar with purified hydrogen during the entire reductive amination step. After cooling the autoclave, the final product was collected, filtered, stripped of excess ammonia, and stripped on a rotary evaporator to remove light amines and water. A total of 350-400 g of low color ether amine mixture was recovered. The analysis results are shown in Table 4.

Example 5 (Comparative): 1 mol glycerin + 6 mol PO, amination a) 1 mol glycerin + 6 mol PO
In a 2 liter autoclave, 276.3 g glycerin and 2.6 g potassium tert. -Butyrate was mixed. The autoclave was purged with nitrogen three times and heated to 140 ° C. Within 10 hours, 1044.0 g of propylene oxide was added. The mixture was left to react at 140 ° C. for 9.5 hours. The reaction mixture was stripped with nitrogen and volatile compounds were removed under vacuum at 80 ° C. The catalyst was removed by adding 21.1 g Macrosorb MP5plus, stirring at 100 ° C. for 2 hours and filtering.

  A pale yellow oil (1300.0 g, hydroxyl number: 320.2 mg KOH / g) was obtained.

b) 1 mol glycerin + 6 mol PO, amination in a 9 liter autoclave in the presence of 200 mL solid catalyst as described in EP 0696572B1 750 mL of the triol mixture obtained in Example 5-a, 1000 mL THF and 1500 g of ammonia was mixed. The catalyst contained nickel, cobalt, copper, molybdenum and zirconium and was in the form of 3 mm × 3 mm tablets. The autoclave was purified with nitrogen, and the reaction was started by heating the autoclave. The reaction mixture was stirred at 205 ° C. for 15 hours and the total pressure was maintained at 250 bar with purified hydrogen during the entire reductive amination step. After cooling the autoclave, the final product was collected, filtered, stripped of excess ammonia, and stripped on a rotary evaporator to remove light amines and water. 720 g of a low color etheramine mixture was recovered. The analysis results are shown in Table 5.

Use as a laundry detergent additive Blue knitted cotton industrial soil swatches, including beef fat, pork fat, sausage fat, bacon oil and Anchore butter, were purchased from Warwick Equest Co., Ltd. without heating ( Wash at 18 ° C.) and select a 59 minute wash cycle and use 75 g of liquid detergent composition LA1 (Table 8) with or without 1.25 g of ether amine additive and hydrochloric acid After the addition of etheramine, the pH was readjusted and washed in a conventional Western European washing machine (Miele Waschachine Softtronic W 2241). The hardness of water was 2.5 mM (Ca ²⁺ : Mg ²⁺ was 3: 1). Using standard colorimetric measurements, L *, a * and b * values were determined for each soil before and after washing. The level of soiling was calculated from the values of L *, a * and b *.

The removal of dirt from the sample was calculated according to the following formula:
Soil removal index (SRI) = _(after ΔE _before -ΔE) * 100 / ΔE _{before
Before} ΔE is the level of dirt before cleaning,
_After ΔE is the level of dirt after cleaning.

Each stain type was reproduced 6 times. The following are average values. The soil level corresponds to the amount of oil on the fiber. The dirt level of the fibers before washing ( _before ΔE) is high, dirt is removed during the washing process, and the dirt level after washing ( _after ΔE) is low. If dirt is better removed, the value _after ΔE is lower and the difference between the value _before ΔE and the value _after ΔE is greater. Thus, the soil removal index value increases with better washing performance.

¹ is a linear alkyl benzene sulfonate salt provided by Northfield Illinois, USA and having an average aromatic carbon chain length of C11 to C12.

² AE3S is a C12-C15 alkyl ethoxy (3) sulfate provided by Stepan, Northfield, Illinois, USA.

³ AE9 is a C12-C14 alcohol ethoxylate provided by Huntsman, Salt Lake City, Utah, USA and having an average degree of ethoxylation of 9.

⁴ NI45-7 is a C14-C15 alcohol ethoxylate provided by Huntsman, Salt Lake City, Utah, USA and having an average degree of ethoxylation of 7.

^{The 5} random graft copolymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and a plurality of polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000, the weight ratio of polyethylene oxide to polyvinyl acetate is about 40:60, and the grafting point is 1 or less per 50 ethylene oxide units.

⁶ is bis ((C2H5O) (C2H4O) n) (CH3) -N + -CxH2x-N +-(CH3) -bis ((C2H5O) (C2H4O) n) (wherein n is 20 to 30) And x is 3 to 8), or compounds having variations of their sulfation or sulfonation.

⁷ is a polyethyleneimine (MW = 600) having 20 ethoxylate groups per —NH group.

⁸ Proteases are available from Genencor International, Palo Alto, California, USA (eg, Purefure Prime®), or Novozymes, Bagsvaard, Denmark (eg, also provided by Liquase®, Coronase®). Good.

⁹ Natalase (R) and Mannaway (R) are all products of Novozymes, Bagsvaard, Denmark.

¹⁰ Suitable complexing agents are diethylenetetraaminepentaacetic acid (DTPA) provided by Dow Chemical, Midland, Michigan, USA, or hydroxyethane diphosphonate (HEDP provided by Solutia, St Louis, Missouri, USA). Or diethylenetriaminepenta (methylphosphonic) acid.

¹¹ Optical brightener 1 was Tinopal® AMS and Optical Brightener 2 was provided by Ciba Specialty Chemicals, Basel, Switzerland.

  A is a liquid detergent composition LA1 (Table 8) without additional etheramine additives.

  B is a liquid detergent composition LA1 (Table 8) having an ether amine as described in Example 1 (1 mol glycerin + 3 mol BuO + 3 mol PO, amination).

  C is a liquid detergent composition LA1 (Table 8) having an ether amine as described in Example 3 (1 mol glycerin + 6 mol BuO, amination).

  D is a liquid detergent composition LA1 (Table 8) having an ether amine as described in Comparative Example 5 (1 mol glycerin + 6 mol PO, amination).

  All three ether amines under test have a 6: 1 alkylene oxide: glycerol molecular ratio. For all five types of oil stains, ether amines (B and C) containing butylene oxide compared to ether amines (D) containing no butylene oxide and liquid detergent compositions (A) containing no ether amine. Shows an excellent cleaning effect.

Claims (16)

Ether amines of general formula (I)

(Where
R is H or ethyl;
k is 0 or 1,
A represents a linear or branched alkylene having C _{2 to} C ₁₈ carbon atoms,
A may be the same or different,
At least one A represents a linear or branched C ₄ -alkylene group;
the sum of x, y and z ranges from 3 to 100;
x is 1 or more, y is 1 or more, z is 1 or more,
Z is NH2 or OH, but at least two Z per molecule are NH2). The ether amine according to claim 1, wherein at least three A represent a linear or branched C ₄ -alkylene group. All A group, a linear or branched C ₄ - ether amine according to claim 1 or 2 represents an alkylene group.   The etheramine according to any one of claims 1 to 3, wherein the sum of x, y and z is in the range of 3 to 30.   The etheramine according to any one of claims 1 to 4, wherein the sum of x, y and z is in the range of 3 to 10.   The ether amine according to any one of claims 1 to 5, wherein Z is NH2.   The ether amine according to claim 1, wherein the ether amine of the general formula (I) is reacted with an acid. A process for producing an ether amine of general formula (I), comprising:
a) reacting glycerin or 1,1,1-trimethylolpropane with C ₄ -alkylene oxide and optionally C ₂ -C ₁₈ -alkylene oxide, wherein glycerin or 1,1,1- The molar ratio of trimethylolpropane to C ₄ -alkylene oxide is in the range of 1: 3 to 1:10, and
b) amination of alkoxylated glycerin or 1,1,1-trimethylolpropane with ammonia.
Including methods. Glycerol or 1,1,1-trimethylolpropane and _{C 4} - the molar ratio of alkylene oxide is 1: 3 to 1: 6 The method of claim 8, wherein the range of. The C ₂ -C 18 _- alkylene oxide, ethylene oxide, propylene oxide or method according to claim 8 or 9 mixtures thereof.   The method according to any one of claims 8 to 10, wherein the amination step is performed in the presence of a catalyst containing copper, nickel or cobalt.   Before being reduced by hydrogen, the catalytically active material of the catalyst contains oxygen compounds of aluminum, copper, nickel and cobalt, and comprises 0.2% to 5.0% by weight of the tin oxygen compound as calculated by SnO. 12. A method according to any one of claims 8 to 11 which is a range.   A method of using the polyetheramine according to any one of claims 1 to 7 for personal care.   A method of using the polyetheramine according to any one of claims 1 to 7 in a shampoo and body soap formulation.   A method of using the polyetheramine according to any one of claims 1 to 7 as a curing agent for an epoxy resin or a reactant in the production of a polymer.   Use of the polyetheramine according to any one of claims 1 to 7 in polyurethane and polyurea and as a thermoplastic polyamide adhesive.